Dyeing of viscose



Patented Apr. 12, 1932 UNITED STATES PATENT OFFICE Wm!) HKNTBICH AND MAXHARDTMANN, OF WIESDORF-ONJHE-RHINE JOSE! HILGEK OI COLOGNE-HULHEIM, ANDRUDOLF KNOGHE, OI LEVERKUBEN-ON- THE-Rm GERMANY, ASSIGNORS 'I'O GENERALANILINE WORKS, INC, 01 NEW YORK, N. Y A GOBPORA'IION OF DELAWARE name orvIscosE ll'o Drawing. Application filed February 26, 1928, Serial No.842,956, and in Germany February 87, me.

The resent invention relates to a process of pro ucing even dyeings onviscose fabrics containing or composed of viscose of irregular physicalor chemical quality and to the 5 dyed fabrics obtainable thereby.

In dyeing viscose fabrics by means of the dyestuffs hitherto in use,streaky uneven dyeings are frequentlyobtained.v This disadvantage is dueto the irregular physical or chemical quality of the commercial viscoseused,- which displa s a very variable afiinity towards one and t e samedyestuif.

In accordance with the present invention,

the disadvantages encountered in the dyeing of viscose fabrics of irreuIar quality with the substantive dyestufi's hitherto employed, can beavoided b effecting the dyelng by means of dyestu s containing, incomplex combination, heavy metals, such as copper, nickel, cobalt,chromium, cadmium, ZlIlC, vanadium and iron.

The azo dyestufis which are capable of forming heavy metal complexcompounds group in the molecule or by having .in or,tho positlon to anazo group a hydroxy-, a caroxylic acid-, an alkoxy-, an aralkoxyor an.aldehyde-group.

The hea metal complex compounds are enerally ibtainable by treating forsome ours the aqueous solution of the dyestuff with an aqueous solutionof a salt of the repective heavy metal. For example, dyestuffs,containing copper or iron, are obtainable by heating an aqueous solutionof the dyestuif with copper sulfate or ferrous sulfate for severalhours, or according to the process described in'the U. S. P. 1,690,782,issued November 6, 1928 b reacting upon the aqueous solution of theyestufi' with a copper-amine compound.

Complex nickel,cob'alt, cadmium or zinc amine azo compounds areobtainable, for example, by the use of nickelous amine salts, such anickelous tetramine sulfate, of cobalt amine salts, such as carbonatotetramine cobalti chloride, or of cadimumor zinc-amine salts, instead ofthe copper amine complex salts used in the prooes of U. S. P. 1,690,782.Dyetufls, containing chromium, are obare distinguished by having asalicyclic.

tainable by boiling the aqueous solution of the dyestufi for severalhours with a water soluble chromium salt, such as chromium formate, andchromium fluoride; com lex vanadium compounds are obtainable by oilingthe dyestuif with a water soluble vanadic acid salt, for example, theammonium salt of the meta vanadic acid.

The dyeing is carried out in the usual manner as is outlined in theexamples, by'dissolving the dyestuffs in hot water and adding to thedye-bath Glaubers salt and monopol soap (alkali metal salt of sulfonatedcastor oil), if desired with the addition of a wetting agent, f. i. analkyl-naphthalene-sulfonic acid, such as iso butyl-napthalene-disulfonicacid. The viscose is introduced into the bath at about 30 0., then thebath is slowly heated to about 80 0., at which temperature the viscoseis dyed for about hour to 1 hour. Then the viscoseiis washed and dried.

The dyeings thus produced on viscose and in particular on knittedartificialv silk by means of the azo dyestuffs containing a heavy metalin complex combination possess a good fastness to light nd aredistinguished by an excellent evenness.

The following examples will illustrate our invention, without limitin itthereto:

. Example 1.2 g. of the yestufi' containing copper in complexcombination, obtainable according to the process of the U. S. P.1,690,782 from amino benzene-2-carboxylic acid,2-phenylamino-5-hydroxy-naphthalene 7-sulfonic acid and tetramine-cupricsulfate and corresponding to the following probable formula:

coon on N=N 1 o H0: (N s): are dissolved in 3 liters of hot water. 100

dyeings, and-ofremarkable fastness to light.

The dyestuff obtainable from amino benzene-2-carboxylic acid and2-benzoyl amino- 5-hydroxynaphthalene-7'-sulfonic acid and coppered insubstance dyes, according to the same process, yellowish red shades; thecopper amine complex compound of the dyestuff obtainable from 2molecules of amino benzene-2-carboxylic acid, the urea of 2-amino-'5-hydroxynaphthalene-7-sulfonic acid and tetramine-cupric sulfate dyesorange red shades; the copper amine complex compound of the dyestufi'obtainable from two molecules of 4-chloro-1-amino benzene-2-carboxylicacid, 5.5'-dihydroxy-2.2'-dinaphthyl ammo- 7.7 -disulfonic acid andtetramine cupric sulfate dyes bluish violet shades. All these dyestuffsyield'dyeings which are ver fast to light and distinguis ed by remarkale evenness.

A violet shade of the same properties is produced by dyeing knittedviscose artificial silk in the manner described with a dyestuffcontaining COPFBI in complex combination and obtained rom5-nitro-2-a-mino-1-methoxy benzene-4-sulfonic acid and 2(4'-methoxybenzoyl)-amino-5-hydroxynaphthalene- 7 -sulfonic acid.

A remarkable even scarlet red dyeing is produced by the use of adyestufi containing co per in complex combination and 0btamed from2-amino-1-phenol glycerine ether and 2- (4'-methy1-benzoyl)-amino-5-hydrox na hthalene-7-sulfonic acid.

nstead of the azo dyestuffs containing a carboxylic group in the orthoposition to the azo group there can also be used quite generally suchdyestuffs as contain the carbonylor hydroxy group in the ortho positionto at least one azo oup; the above mentioned dyestuffs containing amethoxy group in the ortho osition to an azo group can likewise be repaced by dyestuffs, containing in the ortho position to an azo groupother alkyl hydroxy-, aralkyl hydroxyor aryl hydroxy oups, which mayalso be substituted, if esired.

Ewample 2.By means of the dyestuff containing nickel in complexcombination and obtained from 6-amino-1-hydroxy benzene- 2-carboxylicacid, l-amino naphthalene, 1- hydroxy naphthalene-5-sulfonic acid andnlckel tetramine sulfate which dyestufli' probably corresponds to thefollowing formula:

HOOC OH applied to knitted viscose artificial silk in the mannerdescribed in Example 1 with the addition of 1% of isobutyl naphthalenesulfonic acid (calculated on the weight of the material) a completelyeven bluish black dyeing is produced, possessing excellent fastness tolight. The same dyestuff containing cobalt in complex combination yieldsa greenish black shade of similar properties.

Instead of the dyestuffs here specifically described,other dyestuffscontaining nickel and cobalt in complex combination can likewise beused.

I Example 3..,10 kgs. of knitted viscose are SOIH O:

2 of Glaubers salt and 0.2 kg. of soap.

Powerful even green shades of good fastness to light are obtained.

An even pink of good fastness properties is obtained by dyeing in thesame manner as indicated above with a chromium compound of the dyestufffrom diazotized 4-chloro-2-amino henol-6-sulfoni'c acid and 1-(3'-sulfo-pheny )-3'-methyl-5-pyrazolone; the chromium containing dyestuflffrom diazotized 1-amino-2-naphthol-sulfonic acid andlnaphthol-S-sulfonicacid dyes an even clear blue shade; the dyestufi' containing chromiumobtainable from diazotized 2-aminobenzoic acid and2-amino-naphthalene-I-sulfonic acid dyes an even violet tint; the zinccompound prepared from the dyestufi from diazotized 5-nitro-2-aminophenol and 2-(4- methoxyzlphenyl amino) 5 -naphthol-7-sulfonic aci(coupled in the presence of alkali) dyes an even clear violet shade; theco per compound pre ared from the dyestuff rom diazotized5-n1tro-2-aminophenol and 2-(4'- ethoxy-phenyl-amino)-5-naphthol-7-sulfonic acid dyes an even deep reddish blue shade.

We claim:

1. The process which comprises dyeing viscose of different origin withan azodyestuff containing in ortho position to an azo group at least onesubstituent of the oup consisting of hydroxy-, carbox lie aci alkoxy-,aralkoxyand aldehy 0 groups or containing in its molecule at least onesalicylic acid group, containing in complex combination a metal of thegroup consisting of copper, nickel, cobalt, chromium, cadmium, zinc,vanadium and iron.

2. The process which comprises dyeing viscose of different origin withan azodyestufi containing in ortho position to an azo group at least onesubstituent of the group consisting of hydroxy-, carboxylic acid-,alk0xy-, aralkoxyand aldehydo groups or containing in its molecule atleast one salicylic acid group, containing chromium in complexcombination.

3. The process which comprises dyeing viscose of different origin with achromium complex compound of the azodyestuff prepared from diazotized5-nitro-2-aminophenol and 2-naphthylamine-5-sulfonic acid.

4. As new articles of manufacture viscose of diflerent origin dyed withan azodyestuif as claimed in claim 1; the dyeings being distinguished byan excellent evenness.

5. As new products of manufacture viscose of different origin dyed withan azodyestufi' as claimed in c aim 2, the dyeings being distinguishedby an excellent evenness.

6. As a new article of manufacture viscose of different origin dyed withthe azodyestuff as claimed in claim 3, the dyeing being distinguished byan excellent evenness.

In testimony whereof we have hereunto set our hands.

WINFRID HENTRICH. 11. 8.] MAX HARDTMANN. [1,. 5. JOSEF HILGER. [L.S.]RUDOLF KNOCHE. [1,. 5.]

